Classifications

• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
  • C12P13/00—Preparation of nitrogen-containing organic compounds
  • C12P13/02—Amides, e.g. chloramphenicol or polyamides; Imides or polyimides; Urethanes, i.e. compounds comprising N-C=O structural element or polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C233/00—Carboxylic acid amides
  • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
  • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
  • C07C233/09—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to carbon atoms of an acyclic unsaturated carbon skeleton
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S435/00—Chemistry: molecular biology and microbiology
  • Y10S435/8215—Microorganisms
  • Y10S435/822—Microorganisms using bacteria or actinomycetales
  • Y10S435/874—Pseudomonas
  • Y10S435/876—Pseudomonas fluorescens
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S435/00—Chemistry: molecular biology and microbiology
  • Y10S435/8215—Microorganisms
  • Y10S435/911—Microorganisms using fungi
  • Y10S435/939—Rhizopus

Definitions

• the present invention relates to a process for the preparation, by aminolysis of acrylic or methacrylic acid using enzymes, amides functionalized with a cationizable tertiary amine of acrylic or methacrylic acid.
• the invention also relates to the amides of acrylic or methacrylic acid. obtained by said process.
• patent FR 2 259 088 discloses a process in several stages passing through the formation of an intermediate product such as ⁇ -amino-propionamide which is then heat treated at high temperatures. This known method has the drawback of generating undesirable decomposition reactions and of having a low overall yield.
• FR 2 423 482 Another known solution (FR 2 423 482) consists in using a catalyst based on dialkylated tin oxides accelerator of the aminolysis reaction. But such process uses compounds that do not meet the current concerns of environmental and ecological regulations.
• FR 2 590 567 proposes a process reacting an acrylic anhydride or methacrylic on a diamine. But such a method has the disadvantage of leaving an expensive anhydride, difficult to supply and generating as under produces acrylic or methacrylic acid.
• the Applicant has developed a process in a single step for obtaining amides of acrylic acid or methacrylic functionalized by a tertiary amine cationizable with a high overall performance and low rates of side reactions such as polymerization or Micha ⁇ l's reaction while implementing conditions and compounds complying with current standards and / or regulations of the environment.
• one of the aims of the invention is the development of said method allowing the synthesis of the monomer and limiting the formation of products resulting from the reaction by Micha ⁇ l by aminolysis of acrylic or methacrylic esters in the presence of minus a polymerization inhibitor and using enzymes.
• the polymerization inhibitor can be chosen among all the polymerization inhibitors well known to those skilled in the art and in particular among alloocimene, hydroquinone, methyl ether of hydroquinone, phenothiazine, 2,6-terbutyl-p-cresol.
• lipases of various origins such as for example of fungal or bacterial origin or even animal.
• lipases of bacterial or fungal origin mention may be made of lipases of Chromobacterium viscosum, Aspergillus niger, Mucor miehei, Rhizopus arrhizus, Candida cylindracea, Candida antarctica, Rhizopus delemar, Mucor javanicus, from Pseudomonas fluorescens.
• lipases of Chromobacterium viscosum Aspergillus niger, Mucor miehei, Rhizopus arrhizus, Candida cylindracea, Candida antarctica, Rhizopus delemar, Mucor javanicus, from Pseudomonas fluorescens.
• animal lipase we can name the pig pancreas lipase.
• the enzyme (s) used in the process according to the invention are chosen from a Candida antarctica lipase immobilized on a macroporous acrylic type resin known under the name Novozyme® or still well among a Mucor miehei lipase known under the name Lipozyme® or finally their mixtures.
• the acrylic and methacrylic esters are generally chosen from acrylates or alkyl methacrylates and more particularly from methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate.
• reaction according to the invention is carried out at atmospheric pressure and at a temperature between 20 ° C and 100 ° C and preferably between 40 ° C and 90 ° C.
• the crude reaction product obtained after cooling contains acrylamide or N-dialkylamino alkyl or oxyalkyl methacrylamide of formula (I) corresponding to the starting ester, the excess diamine and / or unreacted ester, Micha ⁇ l's reaction products and the enzyme (s) used in during the reaction, these enzymes being recovered by filtration.
• composition of the crude product obtained is determined qualitatively and quantitatively by 1 H NMR analysis of said crude product in solution in deuterated chloroform.
• a preferred embodiment of the invention implements a reaction aminolysis of methyl methacrylate by 3-dimethylaminopropylamine to presence of Novozyme® or Lipozyme® type lipases to obtain 3-dimethylaminopropylmethacrylamide.
• air bubbling displaces the balance by entrainment of methanol formed by the aminolysis reaction and prevents polymerization of the monomers.
• the heating is switched off and agitation is maintained during one hour.
• the product then obtained is cooled to room temperature and then filtered.
• the filtrate is a solution consisting of methyl methacrylate, unreacted amine, methacrylamide formed as well as Michael reaction products.
• the yields are determined relative to the amine used using analysis of the 1 H NMR spectra produced on the solutions of the filtrate in deuterated chloroform.
• the filtrate contains 97% of 3-dimethylaminopropylmethacrylamide and 3% of Micha ⁇ l's products resulting in a strong conversion to amide (97%) and low formation of Micha ⁇ l products (3%).
• the heating is switched off and agitation is maintained during one hour.
• the product obtained is then cooled to room temperature and then filtered.
• the filtrate is a 90% solution of 3-dimethylaminopropylmethacrylamide determined using analysis of 1 H NMR spectra performed on the filtrate in solution in deuterated chloroform, thus showing that it is possible to reduce the air flow rates and amine while retaining a high conversion rate to amide (90%) and a low content of Micha ⁇ l products (10%).
• Example 2 the same compounds are reacted as those used in Example 1 in the presence of half the amount of Novozyme® relative to the mine.
• the heating is switched off and agitation is maintained during one hour.
• a filtrate is then obtained containing 92% of dimethylaminopropyl methacrylamide, 6% of Micha ⁇ l products and 2% of residual amine, composition determined using analysis of 1 H NMR spectra produced on the filtrate in solution in deuterated chloroform thus giving a strong conversion to amide (92%) and a low formation of Micha ⁇ l products (6%).
• the aminolysis reaction of the ester is carried out at 40 ° C.
• air bubbling displaces the balance by entrainment of methanol formed during the aminolysis reaction and prevents polymerization of the monomers.
• the heating is switched off and agitation is maintained during one hour.
• ester aminolysis reaction is carried out at 90 ° C.
• the heating is switched off and agitation is maintained for thirty minutes.
• the product then obtained is cooled to room temperature and then filtered.
• the filtrate is a solution consisting of methyl methacrylate, unreacted amine, formed methacrylamide and products of the Micha ⁇ l reaction.
• the yield calculations are determined using analysis of 1 H NMR spectra performed on the filtrate in solution in deuterated chloroform
• the filtrate contains 83% of 3-dimethylaminopropylmethacrylamide, 16% of Micha ⁇ l products and 1% of residual amine thus resulting in a strong conversion to amide (83%).
• the product then obtained contains 97% of 3-dimethylaminopropylacrylamide and 3% of Micha ⁇ l products determined using analysis of 1 H NMR spectra produced on the filtrate in solution in deuterated chloroform.
• example 1 is reproduced.
• Example 1 a filtrate with the same composition as that of Example 1.
• the filtrate obtained then contains 96% of 3-dimethylaminopropylmethacrylamide and 4% of Micha ⁇ l products determined using analysis of 1 H NMR spectra performed on the filtrate in solution in deuterated chloroform

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• Organic Chemistry (AREA)
• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Zoology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Microbiology (AREA)
• General Chemical & Material Sciences (AREA)
• Biotechnology (AREA)
• Health & Medical Sciences (AREA)
• Biochemistry (AREA)
• Bioinformatics & Cheminformatics (AREA)
• General Engineering & Computer Science (AREA)
• General Health & Medical Sciences (AREA)
• Genetics & Genomics (AREA)
• Preparation Of Compounds By Using Micro-Organisms (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1996
  • 1996-12-13 FR FR9615612A patent/FR2757179B1/fr not_active Expired - Fee Related
• 1997
  • 1997-12-04 EP EP97420225A patent/EP0852262A1/de not_active Withdrawn
  • 1997-12-15 US US08/991,002 patent/US5973203A/en not_active Expired - Fee Related

Patent Citations (5)

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